Trimer catalysts with improved processability and surface cure

ABSTRACT

The present invention provides trimerization catalyst compositions having an α,β-unsaturated carboxylate salt and methods to produce a polyisocyanurate/polyurethane foam using such trimerization catalyst compositions.

BACKGROUND OF THE INVENTION

The present invention relates generally to catalyst systems,compositions comprising catalyst systems, polyisocyanurate/polyurethane(PIR/PUR) foam formulations, and methods of making PIR/PUR foams.

Typically, polyisocyanurate/polyurethane (PIR/PUR) foams are made byreacting a polyol and a polyisocyanate in the presence of a catalyst.Additional additives can be present. PIR/PUR foam products haveexcellent thermal stability and flame resistance. Isocyanurates retaintheir strength to temperatures of about 160° C. and are resistant tomost organic solvents, acids, alkali, ultraviolet light, and humidity.

Certain carboxylate salts, such as, for example, certain alkali metalcarboxylate salts, have been used as catalysts in the production ofPIR/PUR foams. The use of commercially available alkali metalcarboxylate salt catalysts, however, often leads to undesirable foamprocessing problems which are particularly significant in continuousfoam operations. A distinctive “step” is observed, which is normallyassociated with the onset of the trimerization process, when measuringthe rise speed profile of the foam, or by plotting the foam heightversus time. This trimerization “step” causes a significant change inthe speed of the foam rise; in essence, the foam expands at twodifferent rates during the foaming process. In a continuouspolyisocyanurate/polyurethane foam lamination operation, it is difficultto adjust the speed of the production unit to match the change in thespeed of the foam rise. The result can be foam overpacking or foam backflow. This undesirable rapid rise in foam height is particularlytroublesome when processing polyisocyanurate/polyurethane formulationsat a high Isocyanate Index. That is, the change in the rate of foam riseis much more dramatic at a higher Isocyanate Index. Consequently, it isa technical challenge to produce desirable low flammability foamproducts, with a high isocyanate index, when using conventional alkalimetal carboxylate salt catalysts.

As compared to alkali metal carboxylate salt catalysts, commerciallyavailable polyisocyanurate trimerization catalysts based onhydroxyalkylammonium carboxylate salts show different processability incontinuous operations. They provide a smoother rate of rise profile andhave a less significant trimerization “step.” That is, the rate of foamrise is more consistent, even at a higher Isocyanate Index. However,hydroxyalkylammonium carboxylate salt catalysts can be unstable attemperatures above about 100° C., decomposing into volatile amineby-products. This decomposition process causes the release of volatileamines and can impart an undesirable amine odor to finished foamproducts. The polymerization reactions that produce PIR/PUR foam arehighly exothermic, often leading to foam processing temperatures inexcess of 100° C. Hence, hydroxyalkylammonium carboxylate salt catalystscan provide more predictable foam processability, but sometimes at theexpense of a foam product with an undesirable amine odor.

Thus, there exists a need for a catalyst composition that can offer asmooth rise profile—foam height versus time—for producing PIR/PUR foamsin continuous operations. Further, the catalyst composition also shouldperform well in foam formulations with a high Isocyanate Index. At thesame time, the catalyst composition should provide equivalent or fastersurface cure when compared to commercially available catalyst systems,such that the foam products made with the catalyst composition can havereduced surface friability and enhanced surface adherence during themanufacture of finished products such as laminated foam panels.Optionally, depending upon the selection of the catalyst components, thecatalyst composition can be thermally stable at the temperatures whichPIR/PUR foams normally encounter during manufacturing, and produce foamsthat are substantially free of volatile amines and/or amine odors.

BRIEF SUMMARY OF THE INVENTION

The present invention provides a novel catalyst composition forproducing a PIR/PUR foam comprising at least one α,β-unsaturatedcarboxylate salt having the formula

wherein:

X, Y, and Z are selected independently from a C₁-C₃₆ alkyl, alkenyl,aryl, or aralkyl, any of which are substituted or unsubstituted; —CO₂H;—CO₂M; or a hydrogen atom; and

M in each occurrence is selected independently from

-   -   (i) an alkali metal ion,    -   (ii) an alkaline earth metal ion, or    -   (iii) a quaternary ammonium ion.

In another aspect, the present invention discloses a novel compositioncomprising the contact product of at least one activehydrogen-containing compound and a catalyst composition comprising atleast one α,β-unsaturated carboxylate salt. Further, the presentinvention also discloses a novel composition comprising the contactproduct of at least one polyisocyanate and a catalyst compositioncomprising at least one α,β-unsaturated carboxylate salt.

The present invention also provides a method for preparing apolyisocyanurate/polyurethane (PIR/PUR) foam which comprises contactingat least one polyisocyanate with at least one active hydrogen-containingcompound, in the presence of at least one blowing agent and an effectiveamount of a catalyst composition comprising at least one α,β-unsaturatedcarboxylate salt.

The catalyst composition of the present invention offers a substantiallyconsistent foam height rise versus time—even at a high IsocyanateIndex—and provides a faster surface cure during the preparation ofPIR/PUR foams. In another aspect of the present invention, the catalystcomposition can be thermally stable at standard foam processingtemperatures, producing PIR/PUR foams which are substantially free ofvolatile amines and/or amine odors.

Definitions

The following definitions are provided in order to aid those skilled inthe art in understanding the detailed description of the presentinvention.

-   -   PIR—Polyisocyanurate.    -   PUR—Polyurethane.    -   Isocyanate Index—The actual amount of polyisocyanate used        divided by the theoretically required stoichiometric amount of        polyisocyanate required to react with all the active hydrogen in        the reaction mixture, multiplied by 100. Also known as (Eq        NCO/Eq of active hydrogen)×100.    -   pphp—parts by weight per hundred weight parts polyol.    -   DABCO® K15 catalyst from Air Products and Chemicals, Inc. (APCI)        is a 70% solution of an alkali metal carboxylate salt, potassium        2-ethylhexanoate (also known potassium octoate), in diethylene        glycol.    -   DABCO TMR® catalyst from APCl is a 75% solution of        2-hydroxypropyltrimethylammonium octoate in ethylene glycol    -   Polycat® 5 catalyst from APCl is urethane catalyst, known        chemically as pentamethyldiethylenetriamine.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 presents a plot of the normalized foam height versus time forα,β-unsaturated carboxylate salt catalyst 1, the DABCO® K15 catalyst,and the DABCO TMR® catalyst, at an lsocyanate Index of about 270.

FIG. 2 presents a plot of the rate of foam rise speed versus time forα,β-unsaturated carboxylate salt catalyst 1, the DABCO® K15 catalyst,and the DABCO TMR® catalyst, at an Isocyanate Index of about 270.

FIG. 3 presents a plot of the normalized foam height versus time forα,β-unsaturated carboxylate salt catalyst 2, the DABCO® K15 catalyst,and the DABCO TMR® catalyst, at an Isocyanate Index of about 270.

FIG. 4 presents a plot of the normalized foam height versus time forα,β-unsaturated carboxylate salt catalyst 3, the DABCO® K15 catalyst,and the DABCO TMR® catalyst, at an Isocyanate Index of about 270.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to a novel catalyst compositioncomprising at least one α,β-unsaturated carboxylate salt. This novelcatalyst system can be used as a polyisocyanate trimerization catalystsystem for producing polyisocyanurate/polyurethane (PIR/PUR) foams.Further, the present invention also is directed to novel compositionscomprising the contact product of at least one activehydrogen-containing compound and a catalyst composition comprising atleast one α,β-unsaturated carboxylate salt, as well as novelcompositions comprising the contact product of at least onepolyisocyanate and a catalyst composition comprising at least oneα,β-unsaturated carboxylate salt. These novel compositions can be usedtogether with additional components to produce PIR/PUR foams.

Also, the present invention provides a method for preparing a PIR/PURfoam which comprises contacting at least one polyisocyanate with atleast one active hydrogen-containing compound in the presence of atleast one blowing agent and an effective amount of a catalystcomposition comprising at least one α,β-unsaturated carboxylate salt.Additionally, rigid PIR/PUR foams can be produced with the novelcatalyst system of the present invention by several methods known withinthe art.

A catalyst composition comprising at least one α,β-unsaturatedcarboxylate salt can be used to trimerize isocyanates to produceisocyanurates. Generally, any amount of the at least one α,β-unsaturatedcarboxylate salt can be used in the compositions of the presentinvention. As used in practice, catalyst systems for PIR/PUR foamstypically include solutions of carboxylate salts in, for example, adiluent such as ethylene glycol. When a quantity by weight, or by mole,of the catalyst composition of the present invention is discussed, thequantity will exclude the effect of the diluent, unless statedotherwise. As an example, if 10 grams of a 50% solution of potassiumacetate catalyst in ethylene glycol were used in a given application,the amount of the potassium acetate salt catalyst would equal 5 grams.Hence, 5 grams of that catalyst component would be used in calculatingany weight ratios of that component in relation to, for example, theamount of active hydrogen-containing compound or the amount of polyol.

Applicants disclose several types of ranges in the present invention.These include, but are not limited to, a range of temperatures; a rangeof number of atoms; a range of foam density; a range of IsocyanateIndex; and a range of pphp for the blowing agent, water, surfactant,flame retardant, urethane catalyst, and catalyst composition comprisingat least one α,β-unsaturated carboxylate salt. When Applicants discloseor claim a range of any type, Applicants' intent is to disclose or claimindividually each possible number that such a range could reasonablyencompass, as well as any sub-ranges and combinations of sub-rangesencompassed therein. For example, when the Applicants disclose or claima chemical moiety having a certain number of carbon atoms, Applicants'intent is to disclose or claim individually every possible number thatsuch a range could encompass, consistent with the disclosure herein. Forexample, the disclosure that “X” can be an alkyl group having up to 36carbon atoms, or in alternative language a C₁ to C₃₆ alkyl group, asused herein, refers to a “X” group that can be selected independentlyfrom a alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32,33, 34, 35, or 36 carbon atoms, as well as any range between these twonumbers (for example, a C₁ to C₁₈ alkyl group), and also including anycombination of ranges between these two numbers (for example, a C₃ to C₅and C₇ to C₁₀ alkyl group). Likewise, this applies to all other carbonranges disclosed herein, for example, C₁ to C₃₆ ranges for Y and Z;alkoxy groups having up to 10 carbon atoms; etc.

Similarly, another representative example follows for the parts byweight of the catalyst composition comprising at least oneα,β-unsaturated carboxylate salt per hundred weight parts of the atleast one active hydrogen-containing compound in a foam formulation. Ifthe at least one active hydrogen-containing compound is an at least onepolyol, the parts by weight per hundred weight parts polyol is referredto as pphp. Hence, by the disclosure that the catalyst compositioncomprising at least one α,β-unsaturated carboxylate salt is present inan amount from about 0.05 to about 10 pphp, for example, Applicantsintend to recite that the pphp can be selected from about 0.05, about0.06, about 0.07, about 0.08, about 0.09, about 0.1, about 0.2, about0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9,about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8,about 9, or about 10. Likewise, all other ranges disclosed herein shouldbe interpreted in a manner similar to these two examples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that may be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

Another aspect of the present invention provides a thermally stablecatalyst system. When used to describe this feature, a compound isdefined as thermally stable at a given temperature when it does notdecompose or release volatile amines and/or related amine odors at thegiven temperature. A hydroxyalkylammonium salt catalyst, such as theDABCO TMR® catalyst, can become unstable when the PIR/PUR foamtemperature reaches above about 100° C. during foam processing. At theseelevated temperatures, due to the nature of the quaternary amine salt,the DABCO TMR® catalyst can release volatile amine components. Catalystcompositions of the present invention which are based on quaternaryammonium salts are thermally stable if they do not have eitherfunctional groups (e.g., hydroxyl) or hydrogen on the carbon atom at theβ-position relative to the quaternary nitrogen.

Thus, thermally stable catalyst compositions of the present inventioninclude, but are not limited to, alkali metal α,β-unsaturatedcarboxylate salts and alkaline earth metal α,β-unsaturated carboxylatesalts, or any combination thereof. Quaternary ammonium salts withthermal stability include, but are not limited to, tetramethylammoniumacrylate, tetraethylammonium acrylate, tetrapropylammonium acrylate,tetrabutylammonium acrylate, tetramethylammonium methacrylate,tetraethylammonium methacrylate, tetrapropylammonium methacrylate,tetrabutylammonium methacrylate, mono-tetramethylammonium fumarate,bis-tetramethylammonium fumarate, potassium tetramethylammoniumfumarate, mono-tetraethylammonium fumarate, bis-tetraethylammoniumfumarate, potassium tetraethylammonium fumarate,mono-tetrapropylammonium fumarate, bis-tetrapropylammonium fumarate,potassium tetrapropylammonium fumarate, mono-tetrabutylammoniumfumarate, bis-tetrabutylammonium fumarate, potassium tetrabutylammoniumfumarate, mono-potassium maleate, bis-potassium maleate,mono-tetramethylammonium maleate, bis-tetramethylammonium maleate,potassium tetramethylammonium maleate, mono-tetraethylammonium maleate,bis-tetraethylammonium maleate, potassium tetraethylammonium maleate,mono-tetrapropylammonium maleate, bis-tetrapropylammonium maleate,potassium tetrapropylammonium maleate, mono-tetrabutylammonium maleate,bis-tetrabutylammonium maleate, potassium tetrabutylammonium maleate,and the like.

In one aspect of the present invention, the catalyst compositioncomprising at least one α,β-unsaturated carboxylate salt has thermalstability up to about 150° C., wherein no or substantially no volatileamine compounds are emitted. Typical foam temperatures resulting fromthe exothermic reactions during the processing of PIR/PUR foam can be inthe range of about 80° C. to about 150° C. In a further aspect, thecatalyst system of the present invention has thermal stability up toabout 175° C., about 200° C., about 220° C., about 240° C., or about250° C.

The carboxylate salts of the catalyst composition of the presentinvention can be produced, for example, by the reaction of an organicacid with an alkali hydroxide. In another aspect of the presentinvention, the carboxylate salt can be produced by the reaction of anorganic acid with a tetraalkylammonium hydroxide, or a reaction of anorganic acid with a tertiary amine followed by a reaction with an epoxycompound. The latter reaction with an epoxy can lead to a hydroxyalkylquaternary compound which is unstable at elevated temperatures.

Although not a requirement of the present invention, the catalystcomposition can further comprise other catalytic materials orcarboxylate salts in any amount. These include, but are not limited to,alkali metal carboxylate salts, alkaline earth metal carboxylate salts,quaternary ammonium carboxylate salts, or combinations thereof. As oneexample, the optional alkali metal carboxylate salt catalyst ispotassium 2-ethylhexanoate, also known as potassium octoate, and thiscomponent can be present in solution form, such as is commerciallyavailable as the DABCO® K15 catalyst. It is also within the scope of thecatalyst composition of this invention to include mixtures orcombinations of more that one α,β-unsaturated carboxylate salt.Additionally, the catalyst composition of the present invention can alsofurther comprise at least one urethane catalyst.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component of the foamformulations described herein. Combining additional catalyst componentscan be done by any method known to one of skill in the art. For example,in one aspect of the present invention, catalyst compositions can beprepared by combining or contacting the at least one α,β-unsaturatedcarboxylate salt and with an optional alkali metal carboxylate salt.This typically occurs in solution form. In another aspect, the catalystcomposition can be prepared by first mixing the respective carboxylicacids, followed by neutralization to form the corresponding salts.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps.

α,β-Unsaturated Carboxylate Salts

Catalyst compositions of the present invention comprise at least oneα,β-unsaturated carboxylate salt. The at least one α,β-unsaturatedcarboxylate salt is particularly useful for producing PIR/PUR foams.Further, catalyst compositions within the scope of the present inventioncan comprise at least one α,β-unsaturated carboxylate salt having theformula

wherein:

X, Y, and Z are selected independently from a C₁-C₃₆ alkyl, alkenyl,aryl, or aralkyl, any of which are substituted or unsubstituted; —CO₂H;—CO₂M; or a hydrogen atom; and

M in each occurrence is selected independently from

-   -   (i) an alkali metal ion,    -   (ii) an alkaline earth metal ion, or    -   (iii) a quaternary ammonium ion.

Unless otherwise specified, alkyl and alkenyl groups described hereinare intended to include all structural isomers, linear or branched, of agiven structure; for example, all enantiomers and all diasteriomers areincluded within this definition. As an example, unless otherwisespecified, the term propyl is meant to include n-propyl and iso-propyl,while the term butyl is meant to include n-butyl, iso-butyl, t-butyl,sec-butyl, and so forth. Similarly, substituted alkyl, alkenyl, aryl,and aralkyl groups described herein are intended to include substitutedanalogs of a given structure. For example, the substituents on alkyl,alkenyl, aryl, and aralkyl groups can include, but are not limited to,halides; hydroxyl groups; amino groups; alkoxy, alkylamino, ordialkylamino groups having up to 10 carbon atoms; or combinationsthereof.

Non-limiting examples of alkyl groups which can be present in the atleast one α,β-unsaturated carboxylate salt include methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl, and thelike. Examples of alkenyl groups within the scope of the presentinvention include, but are not limited to, ethenyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and the like.Aryl and aralkyl (aralkyl is defined as an aryl-substituted alkyl orarylalkyl) groups include phenyl, alkyl-substituted phenyl, naphthyl,alkyl-substituted naphthyl, and the like. For example, non-limitingexamples of aryl and aralkyl groups useful in the present inventioninclude, but are not limited to, phenyl, tolyl, benzyl, dimethylphenyl,trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl,propyl-2-phenylethyl, and the like.

In one aspect of the present invention, X, Y, and Z are selectedindependently from a hydrogen atom, methyl, ethyl, propyl, butyl,pentyl, hexyl, phenyl, tolyl, benzyl, —CO₂H, or —CO₂M. In anotheraspect, M in each occurrence is an ion of lithium, potassium, sodium,rubidium, magnesium, or calcium, or a quaternary ammonium ion.Quaternary ammonium ions useful in the present invention include, butare not limited to, tetramethylammonium, tetraethylammonium,tetrapropylammonium, tetrabutylammonium,trimethyl(2-hydroxypropyl)ammonium, triethyl(2-hydroxypropyl)ammonium,tripropyl(2-hydroxypropyl)ammonium, tributyl(2-hydroxypropyl)ammonium,trimethyl(2-hydroxyethyl)ammonium, triethyl(2-hydroxyethyl)ammonium,tripropyl(2-hydroxyethyl)ammonium, tributyl(2-hydroxyethyl)ammonium,dimethylbenzyl(2-hydroxypropyl)ammonium,dimethylbenzyl(2-hydroxyethyl)ammonium, and the like, or any combinationthereof. In a further aspect of the present invention, M is a potassiumion.

Salts and mixtures of salts of acrylic acid, methacrylic acid, fumaricacid, maleic acid, and the like, are within the scope of the presentinvention. Suitable α,β-unsaturated carboxylate salts useful in thepresent invention include, but are not limited to, potassium acrylate,tetramethylammonium acrylate, tetraethylammonium acrylate,tetrapropylammonium acrylate, tetrabutylammonium acrylate, potassiummethacrylate, tetramethylammonium methacrylate, tetraethylammoniummethacrylate, tetrapropylammonium methacrylate, tetrabutylammoniummethacrylate, mono-potassium fumarate, bis-potassium fumarate,mono-tetramethylammonium fumarate, bis-tetramethylammonium fumarate,potassium tetramethylammonium fumarate, mono-tetraethylammoniumfumarate, bis-tetraethylammonium fumarate, potassium tetraethylammoniumfumarate, mono-tetrapropylammonium fumarate, bis-tetrapropylammoniumfumarate, potassium tetrapropylammonium fumarate,mono-tetrabutylammonium fumarate, bis-tetrabutylammonium fumarate,potassium tetrabutylammonium fumarate, mono-potassium maleate,bis-potassium maleate, mono-tetramethylammonium maleate,bis-tetramethylammonium maleate, potassium tetramethylammonium maleate,mono-tetraethylammonium maleate, bis-tetraethylammonium maleate,potassium tetraethylammonium maleate, mono-tetrapropylammonium maleate,bis-tetrapropylammonium maleate, potassium tetrapropylammonium maleate,mono-tetrabutylammonium maleate, bis-tetrabutylammonium maleate,potassium tetrabutylammonium maleate, trimethyl(2-hydroxyethyl)ammoniumacrylate, triethyl(2-hydroxyethyl)ammonium acrylate,tripropyl(2-hydroxyethyl)ammonium acrylate,tributyl(2-hydroxyethyl)ammonium acrylate,dimethylbenzyl(2-hydroxypropyl)ammonium acrylate, dimethylbenzyl(2-hydroxyethyl)ammonium acrylate,trimethyl(2-hydroxyethyl)ammonium methacrylate,triethyl(2-hydroxyethyl)ammonium methacrylate,tripropyl(2-hydroxyethyl)ammonium methacrylate,tributyl(2-hydroxyethyl)ammonium methacrylate,dimethylbenzyl(2-hydroxypropyl)ammonium methacrylate,dimethylbenzyl(2-hydroxyethyl)ammonium methacrylate,bis-(trimethyl(2-hydroxyethyl)ammonium) maleate,bis-(triethyl(2-hydroxyethyl)ammonium)maleate,bis-(tripropyl(2-hydroxyethyl)ammonium) maleate,bis-(tributyl(2-hydroxyethyl)ammonium) maleate, bis-(dimethylbenzyl(2-hydroxypropyl)ammonium) maleate,bis-(dimethylbenzyl(2-hydroxyethyl)ammonium) maleate,bis-(trimethyl(2-hydroxyethyl)ammonium) fumarate,bis-(triethyl(2-hydroxyethyl)ammonium) fumarate,bis-(tripropyl(2-hydroxyethyl)ammonium) fumarate,bis-(tributyl(2-hydroxyethyl)ammonium) fumarate,bis-(dimethylbenzyl(2-hydroxypropyl)ammonium) fumarate,bis-(dimethylbenzyl(2-hydroxyethyl)ammonium) fumarate, and the like, orany combination thereof. In another aspect of the present invention, theat least one α,β-unsaturated carboxylate salt is potassium acrylate,tetramethylammonium acrylate, tetramethylammonium maleate, or anycombination thereof.

Polyisocyanates

Polyisocyanates that are useful in the PIR/PUR foam formation processinclude, but are not limited to, hexamethylene diisocyanate, isophoronediisocyanate, phenylene diisocyante, toluene diisocyanate (TDI),diphenyl methane diisocyanate isomers (MDI), hydrated MDI and1,5-naphthalene diisocyanate. For example, 2,4-TDI, 2,6-TDI, andmixtures thereof, can be readily employed in the present invention.Other suitable mixtures of diisocyanates include, but are not limitedto, those known in the art as crude MDI, or PAPI, which contain4,4′-diphenylmethane diisocyanate along with other isomeric andanalogous higher polyisocyanates. In another aspect of this invention,prepolymers of polyisocyanates comprising a partially pre-reactedmixture of polyisocyanates and polyether or polyester polyol aresuitable. In still another aspect, the polyisocyanate comprises MDI, orconsists essentially of MDI or mixtures of MDI's.

The catalyst system and the method of producing PIR/PUR foam of thepresent invention can be used to produce many types of foam. Thiscatalyst system is useful, for example, in the formation of foamproducts for rigid and flame retardant applications, which usuallyrequire a high Isocyanate Index. As defined previously, Isocyanate Indexis the actual amount of polyisocyanate used divided by the theoreticallyrequired stoichiometric amount of polyisocyanate required to react withall the active hydrogen in the reaction mixture, multiplied by 100. Forpurposes of the present invention, Isocyanate Index is represented bythe equation: Isocyanate Index=(Eq NCO/Eq of active hydrogen)×100,wherein Eq NCO is the number of NCO functional groups in thepolyisocyanate, and Eq of active hydrogen is the number of equivalentactive hydrogen atoms.

Foam products which are produced with an Isocyanate Index from about 80to about 500 are within the scope of this invention. In accordance withother aspects of the present invention, the Isocyanate Index is fromabout 100 to about 475, from about 125 to about 450, from about 150 toabout 425, or from about 200 to about 400.

Polyols

Active hydrogen-containing compounds for use with the foregoingpolyisocyanates in forming the polyisocyanurate/polyurethane foams ofthis invention can be any of those organic compounds having at least twohydroxyl groups such as, for example, polyols. Polyols that aretypically used in PIR/PUR foam formation processes include polyalkyleneether and polyester polyols. The polyalkylene ether polyol includes thepoly(alkyleneoxide) polymers such as poly(ethyleneoxide) andpoly(propyleneoxide) polymers and copolymers with terminal hydroxylgroups derived from polyhydric compounds, including diols and triols,These include, but are not limited to, ethylene glycol, propyleneglycol, 1,3-butane diol, 1,4-butane diol, 1,6-hexane diol, neopentylglycol, diethylene glycol, dipropylene glycol, pentaerythritol,glycerol, diglycerol, trimethylol propane, cyclohexane diol, and sugarssuch as sucrose and like low molecular weight polyols.

Amine polyether polyols can be used in the present invention. These canbe prepared when an amine such as, for example, ethylenediamine,diethylenetriamine, tolylenediamine, diphenylmethanediamine, ortriethanolamine is reacted with ethylene oxide or propylene oxide.

In another aspect of the present invention, a single high molecularweight polyether polyol, or a mixture of high molecular weight polyetherpolyols, such as mixtures of different multifunctional materials and/ordifferent molecular weight or different chemical composition materialscan be used.

In yet another aspect of the present invention, polyester polyols can beused, including those produced when a dicarboxylic acid is reacted withan excess of a diol. Non-limiting examples include adipic acid orphathalic acid or phthalic anhydride reacting with ethylene glycol orbutanediol. Polyols useful in the present invention can be produced byreacting a lactone with an excess of a diol, for example, caprolactonereacted with propylene glycol. In a further aspect, activehydrogen-containing compounds such as polyester polyols and polyetherpolyols, and combinations thereof, are useful in the present invention.

Blowing Agents

Blowing agents that can be used alone or in combination in the PIR/PURfoam formation process include, but are not limited to, water, methylenechloride, acetone, chlorofluorocarbons (CFCs), hydrofluorocarbons(HFCs), hydrochlorofluorocarbons (HCFCs), and hydrocarbons. Non-limitingexamples of HFCs include HFC-245fa, HFC-134a, and HFC-365. Illustrativeexamples of HCFCs include HCFC-141b, HCFC-22, and HCFC-123. Exemplaryhydrocarbons include n-pentane, isopentane, cyclopentane, and the like,or any combination thereof.

The amount of blowing agent used can vary based on, for example, theintended use and application of the foam product and the desired foamstiffness and density. In the foam formulation and method for preparinga polyisocyanurate/polyurethane foam of the present invention, theblowing agent is present in amounts from about 10 to about 80 parts byweight per hundred weight parts polyol (pphp), from about 12 to about 60pphp, from about 14 to about 40 pphp, or from about 16 to about 25 pphp.If water is present in the formulation, for use as a blowing agent orotherwise, water is present in amounts up to about 15 pphp. In otherwords, water can range from 0 to about 15 pphp. In another aspect, watercan range from 0 to about 10 pphp, from 0 to about 8 pphp, from 0 toabout 6 pphp, or from 0 to about 4 pphp.

Urethane Catalyst

Urethane catalysts accelerate the reaction to form polyurethanes, andcan be used as a further component of the catalyst system of the presentinvention to produce polyisocyanurate/polyurethane foam. Urethanecatalysts suitable for use herein include, but are not limited to, metalsalt catalysts, such as organotins, and amine compounds, such astriethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole,N-methylmorpholine (commercially available as the DABCO® NMM catalyst),N-ethylmorpholine (commercially available as the DABCO® NEM catalyst),triethylamine (commercially available as the DABCO® TETN catalyst),N,N′-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine (commercially available as the Polycat® 41catalyst), 2,4,6-tris(dimethylaminomethyl)phenol (commercially availableas the DABCO TMR® 30 catalyst), N-methyldicyclohexylamine (commerciallyavailable as the Polycat® 12 catalyst), pentamethyldipropylene triamine(commercially available as the Polycat® 77 catalyst),N-methyl-N′-(2-dimethylamino)-ethyl-piperazine, tributylamine,pentamethyldiethylenetriamine (commercially available as the Polycat® 5catalyst), hexamethyltriethylenetetramine,heptamethyltetraethylenepentamine, dimethylaminocyclohexylamine(commercially available as the Polycat® 8 catalyst),pentamethyldipropylene-triamine, triethanolamine, dimethylethanolamine,bis(dimethylaminoethyl)ether (commercially available as the DABCO® BL19catalyst), tris(3-dimethylamino)propylamine (commercially available asthe Polycat® 9 catalyst), 1,8-diazabicyclo[5.4.0] undecene (commerciallyavailable as the DABCO® DBU catalyst) or its acid blocked derivatives,and the like, as well as any mixture thereof. Particularly useful as aurethane catalyst for foam applications related to the present inventionis the Polycat® 5 catalyst, which is known chemically aspentamethyldiethylenetriamine.

For preparing a polyisocyanurate/polyurethane foam of the presentinvention, the urethane catalyst can be present in the formulation from0 to about 10 pphp, from 0 to about 8 pphp, from 0 to about 6 pphp, from0 to about 4 pphp, from 0 to about 2 pphp, or from 0 to about 1 pphp. Inanother aspect, the urethane catalyst is present from 0 to about 0.8pphp, from 0 to about 0.6 pphp, from 0 to about 0.4 pphp, or from 0 toabout 02 pphp.

Miscellaneous Additives

Depending upon on the requirements during foam manufacturing or for theend-use application of the foam product, various additives can beemployed in the PIR/PUR foam formulation to tailor specific properties.These include, but are not limited to, cell stabilizers, flameretardants, chain extenders, epoxy resins, acrylic resins, fillers,pigments, or any combination thereof. It is understood that othermixtures or materials that are known in the art can be included in thefoam formulations and are within the scope of the present invention.

Cell stabilizers include surfactants such as organopolysiloxanes.Silicon surfactants can be present in the foam formulation in amountsfrom about 0.5 to about 10 pphp, about 0.6 to about 9 pphp, about 0.7 toabout 8 pphp, about 0.8 to about 7 pphp, about 0.9 to about 6 pphp,about 1 to about 5 pphp, or about 1.1 to about 4 pphp. Useful flameretardants include halogenated organophosphorous compounds andnon-halogenated compounds. A non-limiting example of a halogenated flameretardant is trichloropropylphosphate (TCPP). For example,triethylphosphate ester (TEP) and DMMP are non-halogenated flameretardants. Depending on the end-use foam application, flame retardantscan be present in the foam formulation in amounts from 0 to about 50pphp, from 0 to about 40 pphp, from 0 to about 30 pphp, or from 0 toabout 20 pphp. In another aspect, the flame retardant is present from 0to about 15 pphp, 0 to about 10 pphp, 0 to about 7 pphp, or 0 to about 5pphp. Chain extenders such as ethylene glycol and butane diol can alsobe employed in the present invention. Ethylene glycol, for instance, canalso be present in the formulation as a diluent or solvent for thecarboxylate salt catalysts of the present invention.

Polyisocyanurate/Polyurethane Foam Formulation and Process

One aspect of the present invention provides for a compositioncomprising the contact product of at least one activehydrogen-containing compound and a catalyst composition comprising atleast one α,β-unsaturated carboxylate salt. A second aspect provides acomposition comprising the contact product of at least onepolyisocyanate and a catalyst composition comprising at least oneα,β-unsaturated carboxylate salt. In both of these two compositions, thecomposition can further comprise at least one urethane catalyst.Likewise, the compositions can further comprise at least one additiveselected from at least one cell stabilizer, at least one flameretardant, at least one chain extender, at least one epoxy resin, atleast one acrylic resin, at least one filler, at least one pigment, orany combination thereof.

The present invention provides a method for preparing apolyisocyanurate/polyurethane (PIR/PUR) foam which comprises contactingat least one polyisocyanate with at least one active hydrogen-containingcompound, in the presence of at least one blowing agent and an effectiveamount of a catalyst composition comprising at least one α,β-unsaturatedcarboxylate salt. In accordance with the method of the presentinvention, PIR/PUR foams can be produced having a density from about 20Kg/m³ to about 250 Kg/m³ (about 1.25 lb/ft³ to about 15.5 lb/ft³), orfrom about 24 Kg/m³ to about 60 Kg/m³ (about 1.5 lb/ft³ to about 3.75lb/ft³).

In another aspect, the method of the present invention offers asubstantially consistent foam height rise versus time—even at a highIsocyanate Index—that is highly desired for continuous foammanufacturing operations. The method for preparing PIR/PUR foams alsoprovides equivalent or faster surface cure when compared to othercommercially available catalyst systems, such that the PIR/PUR foam hasenhanced surface adherence, useful for the production are articles suchas laminated foam panels.

Optionally, in yet another aspect, the method of the present inventioncan produce PIR/PUR foams with no or substantially no undesirable amineodor. Dependent upon the selection of the specific at least oneα,β-unsaturated carboxylate salt, this method can provide thermalstability at the temperatures which PIR/PUR foams normally encounterduring manufacturing, even those foams formulated with a high IsocyanateIndex. In a further aspect, the method for preparing PIR/PUR foam hasthermally stability up to about 150° C., or about 175° C., or about 200°C., or about 220° C., or about 240° C., or about 250° C. In a stillfurther aspect, the method of the present invention produces PIR/PURfoam that is substantially free of volatile amines and/or amine odors.

The catalyst composition comprising at least one α,β-unsaturatedcarboxylate salt should be present in the foam formulation in acatalytically effective amount. In PIR/PUR foam formulations of thepresent invention, the catalyst composition is present in amounts fromabout 0.05 to about 10 parts by weight per hundred weight parts of theat least one active hydrogen-containing compound, excluding the weightcontribution of the catalyst system diluent. In another aspect, thecatalyst composition is present in amounts from about 0.4 to about 9parts, or from about 0.8 to about 8 parts, by weight per hundred weightparts of the at least one active hydrogen-containing compound. If the atleast one active hydrogen-containing compound is an at least one polyol,the catalyst composition is present in amounts from about 0.05 to about10 parts by weight per hundred weight parts polyol (pphp). In anotheraspect, the catalyst composition is present in amounts from about 0.2 toabout 9.5 pphp, about 0.4 to about 9 pphp, about 0.6 to about 8.5 pphp,or about 0.8 to about 8 pphp.

In accordance with one aspect of the method of the present invention,the components of the foam formulation are contacted substantiallycontemporaneously. For example, at least one polyisocyanate, at leastone active hydrogen-containing compound, at least one blowing agent andan effective amount of a catalyst composition comprising at least oneα,β-unsaturated carboxylate salt, are contacted together. Given thenumber of components involved in PIR/PUR formulations, there are manydifferent orders of combining the components, and one of skill in theart would realize that varying the order of addition of the componentsfalls within the scope of the present invention. As well, for each ofthe different orders of combining the aforementioned components of thefoam formulation, the foam formulation of the present invention canfurther comprise at least one urethane catalyst. In addition, the methodof producing PIR/PUR foams can further comprise the presence of at leastone additive selected from at least one cell stabilizer, at least oneflame retardant, at least one chain extender, at least one epoxy resin,at least one acrylic resin, at least one filler, at least one pigment,or any combination thereof. In one aspect of the present invention, allof the components, including optional components, are contactedsubstantially contemporaneously.

In another aspect of the present invention, a premix of ingredientsother than the at least one polyisocyanate are contacted first, followedby the addition of the at least one polyisocyanate. For example, the atleast one active hydrogen-containing compound, the at least one blowingagent, and the catalyst composition of the present invention arecontacted initially to form a premix. The premix is then contacted withthe at least one polyisocyanate to produce PIR/PUR foams in accordancewith the method of the present invention. In a further aspect of thepresent invention, the same method can be employed, wherein the premixfurther comprises at least one urethane catalyst. Likewise, the premixcan further comprise at least one additive selected from at least onecell stabilizer, at least one flame retardant, at least one chainextender, at least one epoxy resin, at least one acrylic resin, at leastone filler, at least one pigment, or any combination thereof.

One aspect of the present invention provides a method for preparing apolyisocyanurate/polyurethane foam comprising (a) forming a premixcomprising:

i) at least one active hydrogen-containing polyol;

ii) about 10 to about 80 parts by weight per hundred weight parts of thepolyol (pphp) blowing agent;

iii) about 0.5 to about 10 pphp silicon surfactant;

iv) zero to about 10 pphp water;

v) zero to about 50 pphp flame retardant;

vi) zero to about 10 pphp urethane catalyst; and

vii) about 0.05 to about 10 pphp of a catalyst composition comprising atleast one α,β-unsaturated carboxylate salt; and

(b) contacting the premix with at least one polyisocyanate at anIsocyanate Index from about 80 to about 500.

EXAMPLES

The foams of the following examples were produced by adding the catalystof the present invention into a premix of the polyol, flame retardant(TCPP), surfactant, urethane catalyst (Polycat® 5 catalyst), and blowingagent (n-pentane), in a 32-oz (951 ml) metal cup. This composition wasmixed for about 10 seconds (s) at about 6,000 RPM using an overheadstirrer fitted with a 2-inch (5.1 cm) diameter stirring paddle.Sufficient isocyanate was then added to achieve the desired IsocyanateIndex, and the formulation was mixed well for about 6 seconds (s) atabout 6,000 RPM using the same stirrer. The 32-oz cup was droppedthrough a hole in the bottom of a 128-oz (3804 ml) paper cup on a stand.The hole was sized appropriately to catch the lip of the 32-oz cup. Thetotal volume of the foam container was about 160 oz (4755 ml). Foamsapproximated this volume at the end of the foam forming reaction. Foamheight over time was recorded. String gel time and tack free time weremeasured manually with a wooden stick and chronometer. Start time andrise time were determined with automated rate of rise equipment.

In the following examples, various types and quantities of catalystswere used to produce PIR/PUR foams of the present invention. Althoughthe amounts of each catalyst are not the same in these examples, therespective catalyst quantities were chosen to provide similar string geltimes. PIR/PUR foam properties are typically compared at equivalentstring gel times. In these examples, unless otherwise specified, thepphp values listed for the carboxylate salt catalysts exclude theadditional weight of the diluent. Table I lists the components of thefoam formulation and their respective pphp that are used in theexamples.

TABLE I Formulations of Foams in Examples 1-3 (catalyst varied)COMPONENT PARTS (weight) Polyester Polyol 100 TCPP 4.7 Surfactant 1.7Polycat ® 5 catalyst 0.15 n-Pentane 17 Trimer Catalyst Varied IsocyanateIndex Index 270

Inventive Example 1 Comparison of a Potassium Acrylate Catalyst withStandard Catalysts

α,β-unsaturated carboxylate salt catalyst 1 was prepared by dissolvingabout 57.5 grams of KOH in about 200 grams of ethylene glycol. Thesolution was then neutralized by the addition of about 64.8 grams ofacrylic acid. The water from neutralization was then removed at about80° C. under vacuum (about 8 mmHg). The resulting approximate 33%solution of potassium acrylate (about 1.6 pphp or 1.6 grams excludingdiluent; about 14.4 mmol) in ethylene glycol constituted catalyst 1.Foams were made using the standard formulation in Table I at anIsocyanate Index of about 270.

Inventive catalyst 1 was compared with two commercial standards, theDABCO® K15 catalyst (70% potassium octoate solution) and the DABCO TMR®catalyst (75% 2-hydroxypropyltrimethylammonium octoate solution).Approximately 2.1 pphp of the DABCO® K15 catalyst were used; excludingdiluent, this converts to about 1.5 pphp or 1.5 grams (about 8.1 mmol)of potassium octoate. Approximately 2.9 pphp of the DABCO TMR® catalystwere used; excluding diluent, this converts to about 2.2 pphp or 2.2grams (about 8.3 mmol) of 2-hydroxypropyltrimethylammonium octoate.

At a fairly equivalent string gel time, Table II shows foam parameterssuch as start time, string gel time, height of string gel time (HSG),rise time and tack free time, for inventive catalyst 1 and the standardcatalysts. Catalyst 1 provided a shorter tack free time than either theDABCO® K15 catalyst or the DABCO TMR® catalyst. Since tack free time isa measure of surface cure, catalyst 1 has a faster surface cure thaneither commercial standard. Faster surface cure of the foam correlateswith improved surface adhesion in foam laminations. The longer tack freetime of the DABCO® K15 catalyst, an alkali metal carboxylate saltsolution, suggests poorer surface curing and potential surfacefriability and surface adhesion issues in laminated foam operations.

FIG. 1 shows the foam height versus time curves for inventive catalyst1, the DABCO® K15 catalyst, and the DABCO TMR® catalyst. Catalyst 1 hasa uniform slope and minimal plateau that is comparable to, if notsuperior than, that of the DABCO TMR® catalyst(2-hydroxylpropyltrimethylammonium octoate). This consistent increase infoam height versus time is highly desired in continuous foammanufacturing operations.

The general shapes of the curves of inventive catalyst 1 and the DABCOTMR® catalyst are very similar in FIG. 2, further illustrating thatinventive catalyst 1 would have excellent foam processing performancesimilar to that of the DABCO TMR® catalyst. These foam rise speedprofiles indicate a more consistent foam rise over time and improvedfoam production performance in continuous operations. In contrast to theDABCO TMR® catalyst, however, inventive catalyst 1 does not have aminefunctionality and can produce PIR/PUR foams substantially free ofvolatile amines and/or amine odors. Noticeably, the DABCO® K15 catalysthas a long valley in between the two peaks in FIG. 2, indicating thedifferent foam rise speeds associated with foam production using thisalkali metal carboxylate salt catalyst.

Inventive Example 2 Comparison of a Tetramethylammonium AcrylateCatalyst with Standard Catalysts

α,β-unsatured carboxylate salt catalyst 2 was prepared by dissolvingacrylic acid in ethylene glycol, followed by neutralization with anapproximate 25% solution of tetramethylammonium hydroxide in methanol.The methanol and the water from neutralization were then removed atabout 80° C. under vacuum (about 8 mmHg). The resulting approximate 50%solution of tetramethylammonium acrylate (about 2.15 pphp or 2.15 grams,excluding diluent; about 14.8 mmol) in ethylene glycol constitutedcatalyst 2. Foams were made using the standard formulation in Table I atan Isocyanate Index of about 270.

Inventive catalyst 2 was compared with two commercial standard catalystsolutions, the DABCO® K15 catalyst (70% potassium octoate solution) andthe DABCO TMR® catalyst (75% 2-hydroxypropyltrimethylammonium octoatesolution). Approximately 2.1 pphp of the DABCO® K15 catalyst were used;excluding diluent, this converts to about 1.5 pphp or 1.5 grams (about8.1 mmol) of potassium octoate. Approximately 2.9 pphp of the DABCO TMR®catalyst were used; excluding diluent, this converts to about 2.2 pphpor 2.2 grams (about 8.3 mmol) of 2-hydroxypropyltrimethylammoniumoctoate.

As shown in Table II, at a similar string gel time, inventive catalyst 2had a tack free time of about 59 seconds, much shorter than thatachieved with either the DABCO® K15 catalyst or the DABCO TMR® catalyst.As such, catalyst 2 would produce foam with a faster surface cure, lesssurface friability, and subsequently, better adhesion performance inlaminated foam structures, as compared to either the DABCO® K15 catalystor the DABCO TMR® catalyst.

FIG. 3 compares the foam height versus time for inventive catalyst 2,the DABCO® K15 catalyst, and the DABCO TMR® catalyst. Catalyst 2 has themost uniform slope, even more uniform than that of the DABCO TMR®catalyst, indicating that catalyst 2 would have the most consistent foamrise or foam expansion speed during PIR/PUR foam manufacturing.

Inventive Example 3 Comparison of a Tetramethylammonium Maleate Catalystwith Standard Catalysts

α,β-unsaturated carboxylate salt catalyst 3 was prepared by dissolvingmaleic acid in ethylene glycol, followed by neutralization with anapproximate 25% solution of tetramethylammonium hydroxide in methanol.The methanol and the water from neutralization were then removed atabout 80° C. under vacuum (about 8 mmHg). The resulting approximate 50%solution of tetramethylammonium maleate (about 1.5 pphp or 1.5 grams,excluding diluent; about 8 mmol) in ethylene glycol constituted catalyst3. Foams were made using the standard formulation in Table I at anIsocyanate Index of about 270.

Inventive catalyst 3 was compared with two commercial standard catalystsolutions, the DABCO® K15 catalyst (70% potassium octoate solution) andthe DABCO TMR® catalyst (75% 2-hydroxypropyltrimethylammonium octoatesolution). Approximately 2.1 pphp of the DABCO® K15 catalyst were used;excluding diluent, this converts to about 1.5 pphp or 1.5 grams (about8.1 mmol) of potassium octoate. Approximately 2.9 pphp of the DABCO TMR®catalyst were used; excluding diluent, this converts to about 2.2 pphpor 2.2 grams (about 8.3 mmol) of 2-hydroxypropyltrimethylammoniumoctoate.

As shown in Table II, at a similar string gel time, inventive catalyst 3provided a tack free time of about 62 seconds, much shorter than eitherthe DABCO® K15 catalyst or the DABCO TMR® catalyst. Inventive catalyst 3would thus produce a foam product with a faster surface cure and bettersurface adherence during the manufacture of finished products such aslaminated foam panels.

FIG. 4 compares the foam height versus time for inventive catalyst 3,the DABCO® K15 catalyst, and the DABCO TMR® catalyst. Catalyst 3 has aslope that is more uniform than either that of the DABCO® K15 catalystor the DABCO TMR® catalyst. Hence, foam produced with inventive catalyst3 would have the most consistent foam rise or foam expansion speed overtime. This is a useful feature for continuous foam operations, such asthose involving lamination processes.

TABLE II Comparison of inventive catalysts 1-3 to standard catalystsStart String Gel Rise Tack Free Time Time HSG Time Time Catalyst [s] [s][%] [s] [s] ^(a)2.1 pphp DABCO ® K15 14 54 91 72 108 ^(b)2.9 pphp DABCOTMR ® 16 49 91 65 77 ^(c)1.6 pphp Catalyst 1 25 55 77 75 72 ^(c)2.15pphp Catalyst 2 20 48 89 74 59 ^(c)1.5 pphp Catalyst 3 16 45 87 75 62Notes: ^(a)2.1 pphp DABCO ® K15 catalyst including diluent converts toabout 1.5 pphp of potassium octoate salt catalyst excluding diluent.^(b)2.9 pphp DABCO TMR ® catalyst including diluent converts to about2.2 pphp of 2-hydroxypropyltrimethylammonium octoate catalyst excludingdiluent. ^(c)Catalyst 1-3 pphp values exclude the diluent.

The invention claimed is:
 1. A composition comprising the contactproduct of: a) at least one active hydrogen-containing compound; and b)a catalyst composition comprising at least one α,β-unsaturatedcarboxylate salt wherein the at least one α,β-unsaturated carboxylatesalt has the formula:

wherein X, Y, and Z are selected independently from a C₁-C₃₆ alkyl,alkenyl, aryl, or aralkyl, any of which are substituted orunsubstituted; —CO₂H; —CO₂M; or a hydrogen atom; wherein M in eachoccurrence is a tetraalkylammonium ion, selected from the group oftetramethylammonium, tetraethylammonium, tetrapropylammonium,tetrabutylammonium, and combinations thereof.
 2. The composition ofclaim 1, wherein X, Y, and Z are selected independently from a hydrogenatom, methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, tolyl,benzyl, —CO₂H, or —CO₂M.
 3. The composition of claim 1, wherein thetetraalkylammonium ion is tetramethylammonium.
 4. The composition ofclaim 1, wherein the at least one α,β-unsaturated carboxylate salt is asalt of acrylic acid, methacrylic acid, fumaric acid, maleic acid, orany combination thereof.
 5. The composition of claim 1, wherein the atleast one α,β-unsaturated carboxylate salt is, tetramethylammoniumacrylate, tetraethylammonium acrylate, tetrapropylammonium acrylate,tetrabutylammonium acrylate, tetramethylammonium methacrylate,tetraethylammonium methacrylate, tetrapropylammonium methacrylate,tetrabutylammonium methacrylate, mono-tetramethylammonium fumarate,bis-tetramethylammonium fumarate, monotetraethylammonium fumarate,bis-tetraethylammonium fumarate, mono-tetrapropylammonium fumarate,bis-tetrapropylammonium fumarate, mono-tetrabutylammonium fumarate,bis-tetrabutylammonium fumarate, monotetramethylammonium maleate,bis-tetramethylammonium maleate, mono-tetraethylammonium maleate,bis-tetraethylammonium maleate, mono-tetrapropylammonium maleate,bis-tetrapropylammonium maleate, monotetrabutylammonium maleate,bis-tetrabutylammonium maleate, or any combination thereof.
 6. Thecomposition of claim 5, wherein the at least one α,β-unsaturatedcarboxylate salt is, tetramethylammonium acrylate, tetramethylammoniummaleate, or any combination thereof.
 7. The composition of claim 1,further comprising at least one urethane catalyst.
 8. The composition ofclaim 1, further comprising at least one additive selected from at leastone cell stabilizer, at least one flame retardant, at least one chainextender, at least one epoxy resin, at least one acrylic resin, at leastone filler, at least one pigment, or any combination thereof.
 9. Thecomposition of claim 1, wherein the catalyst composition comprising atleast one α,β-unsaturated carboxylate salt is thermally stable at atemperature up to about 150° C.
 10. The composition of claim 1, whereinthe at least one active hydrogen-containing compound is at least onepolyether polyol, at least one polyester polyol, or any combinationthereof.
 11. A composition comprising the contact product of: (a) atleast one polyisocyanate; and (b) a catalyst composition comprising atleast one α,β-unsaturated carboxylate salt wherein the at least oneα,β-unsaturated carboxylate salt has the formula:

wherein X, Y, and Z are selected independently from a C₁-C₃₆ alkyl,alkenyl, aryl, or aralkyl, any of which are substituted orunsubstituted; —CO₂H; —CO₂M; or a hydrogen atom; wherein M in eachoccurrence is a tetraalkylammonium ion, selected from the group oftetramethylammonium, tetraethylammonium, tetrapropylammonium,tetrabutylammonium and combinations thereof.
 12. The composition ofclaim 11, wherein the at least one polyisocyanate comprises diphenylmethane diisocyanate.